Method for making a dual curable ethylene propylene diene polymer rubber coating using a photoinitiator and a peroxide

ABSTRACT

A durable ambient light curable waterproof liquid rubber coating with volatile organic compound (VOC) content of less than 450 grams per liter made from ethylene propylene diene terpolymer (EPDM) in a solvent, a photoinitiator, an additive, pigments, and fillers, and a co-agent and a method for making the formulation, wherein the formulation is devoid of thermally activated accelerators.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to and the benefit of U.S.Provisional Patent Application Ser. No. 61/764,471 filed on Feb. 13,2013, entitled “AMBIENT LIGHT CURABLE ETHYLENE PROPYLENE DIENE MONOMERRUBBER COATING DEVOID OF THERMALLY ACTIVATED ACCELERATORS”; U.S.Provisional Patent Application Ser. No. 61/764,479 filed on Feb. 13,2013, entitled “DUAL CURABLE ETHYLENE PROPYLENE DIENE MONOMER RUBBERCOATING USING A PHOTOINITIATOR AND A PEROXIDE”; and U.S. ProvisionalPatent Application Ser. No. 61/764,483 filed on Feb. 13, 2013, entitled“HIGH SOLIDS LOW VOC CONTENT ETHYLENE PROPYLENE DIENE RUBBER COATING.”These references are hereby incorporated in their entirety.

FIELD

The present embodiments generally relate to a method for making ethylenepropylene diene terpolymer rubber coating compositions that are consumerfriendly to use and require no additional mixing of a curing agent.

BACKGROUND

A need exists for a method for making an ambient temperature waterproofrubber coating that cures without the need for blending an additionalcomponent.

A need exists for a method for making an ambient temperature waterproofrubber coating that requires no active heat for curing.

A further need exists for a method for making an ethylene propylenediene terpolymer (EPDM) waterproof rubber coating formed from a liquidthat does not require isocyanates or similar toxic chemicals.

A need exists for a method for making a formulation that can be appliedto existing roofs and existing substrates as a “cool white easilyapplied waterproof rubber coating” to lower the costs of energy andreduce maintenance costs of a facility.

The present embodiments meet these needs.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Before explaining the present method in detail, it is to be understoodthat the method is not limited to the particular embodiments and that itcan be practiced or carried out in various ways.

The present embodiments generally relate to a method for making ethylenepropylene diene terpolymer rubber coating compositions that are consumerfriendly to use and require no additional mixing of a curing agent as atwo component system.

The present embodiments relate to a method for making a durable ambientlight curable waterproof liquid rubber coating with volatile organiccompound (VOC) content of less than 450 grams per liter, such as withoutbenzene or xylene.

A benefit of the method is that the liquid rubber coating produced fromthe method is ambient temperature curable and devoid of thermallyactivated accelerators, so that through simple exposure to ambientlight, the liquid rubber coating curing is initiated without the need toadd an additional component or to add active heat to cure the rubberformulation.

A benefit of the method is that the liquid EPDM formulation produced bythe method is easy to apply in the field since it is a liquid and noheat source is needed to cure the formulation.

A benefit of the method is that users of the liquid EPDM formulationproduced by the method will avoid the possibility of having second orthird degree burns from applying the composition, because the coating is“heat free” to cure on a substrate which can be a roofing tile or flatroof base material. The formulation produced from the method does not“hold heat” but reflects heat.

A liquid EPDM formulation produced from the method creates a curedcoating that has (1) waterproof sealing to resist hurricane strengthrainfall; (2) resistance to acid rain degradation allowing at least 15years useful life for a roof in an acid rain area; (3) ability towithstand cold temperatures of down to −50 degrees Centigrade, such asArctic weather.

A durable ambient light curable waterproof rubber liquid coatingformulation produced from the method does not require isocyanates orsimilar toxic curing agents which are known to have a harmful effect onpeople as evidenced by allergic sensitization to isocyanates.

A durable ambient light curable waterproof liquid rubber coatingformulation produced from the method can be applied to existing roofsand existing substrates as a “cool white roof” material lowering thecost of building maintenance, lowering the cost of energy, and reducingthe dependence of the United States on foreign oil.

Schools, hospitals, public housing facilities, warehouses, residentialhomes, and facilities for the elderly can benefit from a durable ambientlight curable waterproof liquid rubber coating formulation produced fromthe method, on the roofs of their institutions because the material willremain cool, while simultaneously sealing the roof, providing areflective surface to reduce costs of energy and costs of maintainingthe facilities.

A cured material produced from the method can extend the life of a roof,reducing the need for roof replacement.

In other embodiments, the formulation produced from the method can beused to seal docks for marinas.

Another benefit of the method is that the crosslinking reaction creatingcured material is initiated in the presence of ambient light which canbe a light frequency that is visible, ultraviolet, or infrared, causingthe formulation produced from the method to be simple to use.

The method saves time in application of the coating as no additionalequipment is needed to mix the formulation produced from the methodprior to application on the roof substrate, the dock, or anotherintended substrate.

A benefit of a durable ambient light curable waterproof liquid rubbercoating formulation produced from the method is that the invention isstable in its packaging system for delivery to a user.

The following terms are used herein:

The term “active heating” as used herein can refer to the externaladdition of energy to the formulation by the use of heat generatingdevices, such as adding energy through mechanical means with heatedapplication hoses, infrared lamps, heat guns, or by adding heat using anextruder.

The term “additive” as used herein can refer to an antioxidant, anultraviolet light stabilizer, or combinations thereof.

The term “adhesion promoter” as used herein can refer to a componentmade from molecules that tie the formed ambient light curable EPDMcoating to a substrate for enhanced bonding. An example of an adhesionpromoter can be SARET® 633 or 634 made by Arkema France.

The term “air release agent” can refer to mineral oil, paraffinic oil,silicone oil, or similar oil. An example of paraffinic oil can be FHRULTRA® made by Flint Hills Resources of Wichita, Kans., an example of amineral oil can be UNIQFORM™ made by UniqChem UK Co., Ltd., and anexample of an air release agent can be BYK®-320 made by BYK-Chemie GmbHof Germany.

The term “ambient light” as used herein can refer to visible,ultraviolet or near infrared light. The range of wavelength fromultraviolet to near infrared light can range in wavelength from 200nanometers to 1500 nanometers.

The term “ambient temperature” as used herein can refer to a temperatureless than 50 degrees Celsius and equal to or greater than −10 degreesCelsius.

The term “antioxidant” can refer to a hindered phenolic stabilizer, suchas IRGANOX® 1076 made by Ciba Specialty Chemicals Corporation ofTarrytown, N.Y.

The term “anti-settling agent” as used herein can refer to an agent thatprevents the settling of pigments and fillers in a liquid formulation.An example of a usable anti-settling agent can be M-P-A® made byElementis Specialties, Inc. of Hightstown, N.J. Another example is ahydroxyethyl cellulose. Still another example is a fumed silica.

The term “biocide” can be a variety of ingredients. Amethylchloroisothiazolinone, such as MERGAL® K9N made by TroyCorporation or ROCIMA™ 363 available from Dow Chemical of Midland, Mich.can be used.

The term “co-agent” as the term is used herein can refer to a reactivemolecule with two or more functional groups, for bonding with an EPDMmolecule. The co-agent can enhance crosslinking between two EPDMmolecules initiated by a photoinitiator. The term “enhances” can referto an accelerated process of crosslinking. Co-agent accelerates reactionof the free radicals with the active sites of the unsaturated diene tocross link the terpolymer.

Usable co-agents can include an acrylate such as hexane diol diacrylate,polybutadiene acrylate, a triallyl cyanurate, polybutadiene, andphenylenedimaleimide known as VAMAC® DP HVA-2 available from E.I. DuPontof Wilmington, Del.

The term “defoamer” as used herein can refer to components, such aspolymethyl alkyl siloxane. An example of a defoamer can be BYK®-A500defoamer. Defoamers can include modified polysiloxane orpolymethylsiloxane in solvents such as BYK®-066 N or BYK®-052 made byBYK-Chemie GmbH of Germany.

The term “flame retardant” as referred to herein can refer to a liquidor a powder flame retardant. The powdered version can be used in themethod at a different blending point than the liquid version. An exampleof a flame retardant usable herein is alumina trihydrate. Flameretardants can be used as fillers in this invention. Flame retardantscan be used as pigments in this invention.

The term “inert atmosphere” as used herein can refer to an atmosphereplaced over the reaction using an inert gas such as nitrogen or argon.

The term “low shear” as used herein can refer to mixing at a blade tipspeed of less than 2500 linear feet per minute used in the mixingdevice.

The term “molecular weight” for the polymer as used herein can refer toa weight average molecular weight as determined by gel permeationchromatography (GPC) measurement.

The term “photoinitiator” as used herein can refer to photoinitiatorsthat are devoid of thermally activated accelerators.

Usable photoinitiators include type I photoinitiators which can include:bis(2,4,6-trimethylbenzoyl)-phenyl phosphineoxide, known as IRGACURE®819 and 1-hydroxy-cyclohexyl-phenyl-ketone known as IRGACURE® 184 madeby BASF Corporation.

Type II photoinitiators can be usable and can include benzophenone,alpha hydroxyl ketone, alpha amino ketone, isothioxanthone, andcombinations thereof. All photoinitiators can remain devoid of thermallyactivated accelerators.

The term “peroxide” can refer to a chemical compound containing anoxygen-oxygen single bond or the peroxide anion. Examples of usableperoxides include a peroxyketal, a peroxyester, a dialkyl peroxide, aperoxy carbonate, or an azo initiator.

The term “pigment dispersant” can refer to a chemical that allowspigment to remain homogenously dispersed in the coating. Examples ofusable pigment dispersants include NUOSPERSE® 9100 available fromElementis Specialties, Inc.

The term “plant-based solvent” can refer to vegetable based, grassbased, weed based, nut based, or food based solvents including but notlimited to methyl soyate. Only solvents that dissolve EPDM or one of theother polymers are usable herein.

The term “plasticizer” as used herein can refer to non-volatileplasticizers, including paraffinic oil, silicone oil, naphthenic oil,plant based oil, diester oil, mineral oil, a low molecular weightpolyalpha olefin, or combinations thereof.

The term “terpolymer” as used herein can refer to a polymer of ethylene,propylene, and one or more non-conjugated dienes. Examples ofnon-conjugated diene usable herein can include norbornene, ethylidenenorbornene, 1,4, hexadiene, dicyclopentadiene, vinyl norbornene,methylene norbornene, and combinations thereof.

In other embodiments, the terpolymer of ethylene, propylene and one ormore non-conjugated dienes can have the propylene replaced by anotheralpha olefin, such as but not limited to 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, or combinations thereof.

In embodiments, the “polymer” can be ethylene propylene polymer,ethylene butene polymer, ethylene pentene polymer, or combinationsthereof.

“Solvents” as the term is used herein can refer to an aliphatic solvent,an aromatic solvent, or a plant based solvent with a density from 0.6 to1.2 grams per cubic centimeter. Examples of usable solvents includemineral spirits, toluene, hexane, xylene, hexamethyldi-siloxane, orcombinations thereof.

The term “thermally activated accelerator” as the term is used hereincan refer to accelerators which require temperatures above ambienttemperatures to cure an EPDM coating and specifically require “activeheating.”

In a formulation produced by the method, no thermally activatedaccelerators are used, which is a feature of this method.

The term “ultraviolet stabilizers” can refer to chemicals such ashindered amine light stabilizers, benzotriazoles, or similar components.

The term “waterproof” as used herein can refer to a moisture vaporpermeation rating of less than 1.

The term “wetting agent” can refer to chemicals such as DISPONE™ 983available from Elementis Specialties, Inc.

Wetting agents can include silicone polyacrylate copolymer in solventssuch as BYK®-3550 or a solvent-free polyether modifieddimethylpolysiloxane such as BYK®-378 made by BYK-Chemie GmbH ofGermany.

A formulation produced by the method can be coated onto varioussubstrates. Substrates that are usable with this formed ambient lightcurable waterproof liquid rubber coating can include roofs, aged PVCmaterials, aged EPDM roofing materials, aged thermoplastic olefinmaterials, metal, glass, car port roofs, docks, concrete, polyurethanefoam, acrylate material system, wood, oil rig mats, and high impactdevices.

The embodiments can include a method for making a durable ambient lightcurable waterproof liquid rubber formulation with a volatile organiccompound (VOC) content of less than 450 grams per liter.

The method involves blending in a closed vessel forming a solution, afirst portion of ethylene propylene diene terpolymer (EPDM) with a firstportion of solvent, wherein the ethylene propylene diene terpolymer(EPDM) is 50 weight percent to 99 weight percent of a total amount ofethylene propylene diene terpolymer used in a resulting durable ambientlight curable waterproof liquid rubber formulation and the first portionof solvent is 33 weight percent to 67 weight percent of a total amountof solvent used in the resulting durable ambient light curablewaterproof liquid rubber formulation.

The second step involves mixing the solution in a high shear mixer forat least 10 to 240 minutes at a temperature from 20 degrees Celsius to50 degrees Celsius forming a high viscosity solution.

As a third step, a second portion of ethylene propylene diene terpolymer(EPDM) is added to the high viscosity solution, wherein the secondportion of ethylene propylene diene terpolymer (EPDM) is 0.1 weightpercent to 50 weight percent of the total amount of ethylene propylenediene terpolymer (EPDM) used in the resulting durable ambient lightcurable waterproof liquid rubber formulation.

Next, a second portion of solvent is added to the high viscositysolution wherein the second portion of solvent is 33 weight percent to80 weight percent of a total amount of solvent used in the resultingdurable ambient light curable waterproof liquid rubber formulation.

As a fifth step, the high viscosity solution is blended for 10 minutesto 120 minutes at a temperature from 20 degrees Celsius to 50 degreesCelsius to form a low viscosity liquid intermediate rubber formulationwith a saturated backbone of propylene, a saturated backbone ofethylene, and an unsaturated diene with ultra violet activated sitescapable of crosslinking with or reacting with a free radical or a freeradical on another terpolymer.

For a sixth step, 0.1 weight percent to 10 weight percent of aphotoinitiator devoid of thermally activated accelerators is added tothe low viscosity liquid intermediate rubber formulation based on thetotal weight of the resulting dual curable waterproof liquid rubberformulation to generate free radicals that react with the active sitesof the unsaturated diene, forming a low viscosity liquid intermediaterubber formulation with photoinitiator;

As a seventh step, 0.1 to 15 weight percent of a peroxide is added tothe a low viscosity liquid intermediate rubber formulation withphotoinitiator, wherein the peroxide comprises at least one of: aperoxyketal, a peroxyester, a dialkyl peroxide, a peroxy carbonate, oran azo initiator forming a dual cure liquid; and

As the eighth step, the dual cure liquid is blended at a low shear for10 minutes to 120 minutes at a temperature from 20 degrees Celsius to 50degrees Celsius in the absence of light forming the dual curablewaterproof liquid rubber formulation, wherein the dual curablewaterproof liquid rubber formulation is adapted to form a waterproofseal on a substrate in the presence of ultraviolet light and heat.

It is contemplated that temperatures above 50 degrees Celsius can beutilized, but this may result in the undesirable effect of flashevaporating the solvent component.

In embodiments, the method can also involve mixing the photoinitiatorsin a photoinitiator solvent prior to adding the photoinitiators to thelow viscosity liquid intermediate rubber formulation, wherein thephotoinitiator solvent is from 1 weight percent to 20 weight percentbased on the total solvent content of the resulting durable ambientlight curable waterproof liquid rubber formulation. The photoinitiatorsolvent can be a toluene, a xylene, a naphthalene, or a similar organicsolvent.

Photoinitiators include Type I photoinitiators including:bis(2,4,6-trimethylbenzoyl)-phenyl phosphineoxide, and1-hydroxy-cyclohexyl-phenyl-ketone.

Photoinitiators include Type II photoinitiators including benzophenone,alpha hydroxyl ketone, alpha amino ketone, isothioxanthone, andcombinations thereof. All photoinitiators are devoid of thermallyactivated accelerators.

In embodiments, the first portion of ethylene propylene diene terpolymercan have a different molecular weight than the second portion ofethylene propylene diene terpolymer.

In other embodiments, the method can involve adding to the highviscosity solution, at a temperature from 20 degrees Celsius to 50degrees Celsius, at least one of (a) 50 weight percent to 99 weightpercent of a pigment, and (b) 50 weight percent to 99 weight percent ofa filler.

The amount of the pigment and the filler added represent a total weightpercent of pigment and filler in the high viscosity solution.

The method involves blending the pigment and filler to a particledispersion from 4 to 8 units on the Hegman scale.

In further embodiments, this method can involve adding to the lowviscosity liquid intermediate 0.1 weight percent to 10 weight percent ofadditives based on a total weight of the resulting durable ambient lightcurable waterproof liquid rubber formulation.

The additives can be a hindered phenolic stabilizer or a hindered amineultraviolet stabilizer.

The method can also involve adding to the low viscosity liquidintermediate 0.1 weight percent to 10 weight percent of an adhesionpromoter based on the total weight of the resulting durable ambientlight curable waterproof liquid rubber formulation after adding thesecond portion of EPDM to the high viscosity solution.

The adhesion promoter can be a zinc diacrylate or a zinc dimethacrylate.

In embodiments, the method can involve adding to the low viscosityliquid intermediate rubber formulation: 0.1 weight percent to 10 weightpercent of a pigment dispersant based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

In embodiments, the pigment dispersant can be 1 methoxy-2-propylacetate.

In further embodiments, the method can involve adding to the lowviscosity liquid intermediate rubber formulation: 0.1 weight percent to10 weight percent of an anti-settling agent based on the total weight ofthe resulting durable ambient light curable waterproof liquid rubberformulation.

The anti-settling agent can be a hydroxylethyl cellulose and a fumedsilica.

In other embodiments, the method can involve adding to the low viscosityliquid intermediate rubber formulation 0.1 weight percent to 10 weightpercent of a defoamer based on the total weight of the resulting durableambient light curable waterproof liquid rubber formulation.

The defoamer can be a polymethyl alkyl siloxane, a modifiedpolysiloxane, and a polymethylsiloxane in a solvent.

In embodiments, the method can involve adding to the low viscosityliquid intermediate rubber formulation 0.1 weight percent to 10 weightpercent of an air release agent based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

The air release agent can be a mineral oil, a paraffinic oil, a siliconeoil, or a similar oil.

In further embodiments, the method can involve adding 0.1 weight percentto 30 weight percent of a flame retardant to low viscosity liquidintermediate rubber formulation, based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

The flame retardant can be an alumina trihydrate. Flame retardants canbe added to: a pigment, or a filler, and optionally an additive and thento the low viscosity liquid intermediate rubber formulation or after thesecond portion of ethylene propylene diene terpolymer is added to thehigh viscosity solution.

In still more embodiments, the method can involve adding to the lowviscosity liquid intermediate rubber formulation 0.1 weight percent to12 weight percent of a wetting agent based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

The wetting agent can be a silicone polyacrylate copolymer in solventand a solvent-free polyether modified dimethylpolysiloxane.

The method can also involve adding to the low viscosity liquidintermediate rubber formulation 0.1 weight percent to 10 weight percentof a biocide based on the total weight of the resulting durable ambientlight curable waterproof liquid rubber formulation.

In embodiments, the biocide can be a methylchloroisothiazolinone.

In embodiments, the method can involve adding 0.1 weight percent to 30weight percent of a low molecular weight non-volatile plasticizer lowviscosity liquid intermediate rubber formulation after the secondportion of solvent is added to the high shear mixture.

The low molecular weight non-volatile plasticizer can be a paraffinicoil, naphthenic oil, plant based oil, diester oil, silicone oil, amineral oil, a low molecular weight polyalphaolefin, or combinationsthereof.

In embodiments, 0.01 weight percent to 10 weight percent of a co-agentcan be added to the low viscosity liquid intermediate rubber formulationbased on a total weight of the resulting dual curable waterproof liquidrubber formulation of a co-agent to the second low viscosity liquidintermediate rubber formulation.

The co-agent can be an acrylate, a triallyl cyanurate, a polybutadiene,or a phenylenedimaleimide.

In embodiments, the solvents can be selected from the group: mineralspirits and hexamethyldi-siloxane.

In embodiments, the first and second solvent portions can be differentsolvents.

The invention can include creating a special waterproof formulation withlow volatile organic compound content. The volatile organic compoundcontent can be less than 450 and as low as 0.1 volatile organic contentgrams per liter.

The invention relates to a durable ambient light curable waterproofliquid rubber formulation with a volatile organic compound content ofless than 450 grams per liter.

The formulation includes a low viscosity liquid intermediate rubberformulation with a saturated backbone of propylene, a saturated backboneof ethylene, and an unsaturated diene with ultra violet activated sitescapable of crosslinking with or reacting with a free radical or a freeradical on another terpolymer.

The low viscosity liquid intermediate rubber formulation contains afirst portion of ethylene propylene diene terpolymer (EPDM).

The ethylene propylene diene terpolymer (EPDM) is 50 weight percent to99 weight percent of a total amount of ethylene propylene dieneterpolymer.

The low viscosity liquid intermediate rubber formulation contains afirst portion of solvent.

The first portion of solvent is 33 weight percent to 67 weight percentof a total amount of solvent used in the resulting durable ambient lightcurable waterproof liquid rubber formulation.

The low viscosity liquid intermediate rubber formulation contains asecond portion of ethylene propylene diene terpolymer (EPDM).

The second portion of ethylene propylene diene terpolymer (EPDM) is 0.1weight percent to 50 weight percent of the total amount of ethylenepropylene diene terpolymer (EPDM).

The low viscosity liquid intermediate rubber formulation contains asecond portion of solvent.

The second portion of solvent is 33 weight percent to 80 weight percentof a total amount of solvent used in the resulting durable ambient lightcurable waterproof liquid rubber formulation.

To the low viscosity liquid intermediate rubber formulation is added 0.1to 15 weight percent of a peroxide.

The peroxide is based upon the total weight of the resulting dualcurable waterproof liquid rubber formulation.

The peroxide can be a peroxyketal, a peroxyester, a dialkyl peroxide, aperoxy carbonate, or an azo initiator.

To the low viscosity liquid intermediate rubber formulation is added 0.1weight percent to 10 weight percent of a photoinitiator devoid ofthermally activated accelerators to the low viscosity liquidintermediate rubber formulation to generate free radicals that reactwith the active sites of the unsaturated diene.

The formulation creates a durable ambient light curable waterproofliquid rubber formulation devoid of thermally activated accelerators andadapted to crosslink and form a waterproof seal on a substrate only inthe presence of ultraviolet light.

In embodiments, the formulation includes Type I photoinitiatorsincluding: bis(2,4,6-trimethylbenzoyl)-phenyl phosphineoxide, and1-hydroxy-cyclohexyl-phenyl-ketone.

In embodiments, the formulation includes Type II photoinitiatorsincluding benzophenone, alpha hydroxyl ketone, alpha amino ketone,isothioxanthone, and combinations thereof, wherein all photoinitiatorsare devoid of thermally activated accelerators.

In embodiments, the first portion of ethylene propylene diene terpolymercan have a different molecular weight than the second portion ofethylene propylene diene terpolymer.

In embodiments, the formulation includes at least one of: 50 weightpercent to 99 weight percent of a pigment, and 50 weight percent to 99weight percent of a filler.

In embodiments, the amount of the pigment and the filler added representa total weight percent of pigment and filler in the durable ambientlight curable waterproof liquid rubber formulation.

The pigment and filler can have a particle dispersion from 4 to 8 unitson the Hegman scale.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of additives based on a total weight of the resulting durableambient light curable waterproof liquid rubber formulation.

The additives can be a hindered phenolic stabilizer or a hindered amineultraviolet stabilizer.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of an adhesion promoter based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation after adding the second portion of ethylene propylene dieneterpolymer (EPDM) to the high viscosity solution.

The adhesion promoter can be a zinc diacrylate or zinc dimethacrylate.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of a pigment dispersant based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

In embodiments, the pigment dispersant can be 1 methoxy-2-propylacetate.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of an anti-settling agent based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

The anti-settling agent can be a hydroxylethyl cellulose and a fumedsilica.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of a defoamer based on the total weight of the resulting durableambient light curable waterproof liquid rubber formulation.

The defoamer can be a polymethyl alkyl siloxane, a modifiedpolysiloxane, and a polymethylsiloxane in a solvent.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of an air release agent based on the total weight of theresulting durable ambient light curable waterproof liquid rubberformulation.

The air release agent can be a mineral oil, a paraffinic oil, a siliconeoil, or a similar oil.

In embodiments, the formulation includes 0.1 weight percent to 30 weightpercent of a flame retardant to low viscosity liquid intermediate rubberformulation, based on the total weight of the resulting durable ambientlight curable waterproof liquid rubber formulation.

In embodiments, the flame retardant can be an alumina trihydrate.

In embodiments, the formulation includes 0.1 weight percent to 12 weightpercent of a wetting agent based on the total weight of the resultingdurable ambient light curable waterproof liquid rubber formulation.

The wetting agent can be a silicone polyacrylate copolymer in solventand a solvent-free polyether modified dimethylpolysiloxane.

In embodiments, the formulation includes 0.1 weight percent to 10 weightpercent of a biocide based on the total weight of the resulting durableambient light curable waterproof liquid rubber formulation.

In embodiments, the biocide can be a methylchloroisothiazolinone.

In embodiments, the formulation can include 0.1 weight percent to 30weight percent of a low molecular weight non-volatile plasticizer lowviscosity liquid intermediate rubber formulation.

The low molecular weight non-volatile plasticizer can be a paraffinicoil, naphthenic oil, plant based oil, diester oil, silicone oil, amineral oil, a low molecular weight polyalphaolefin, or combinationsthereof.

In embodiments, the formulation can include 0.01 weight percent to 10weight percent of a co-agent based on a total weight of the dual curablewaterproof liquid rubber formulation.

The co-agent can include an acrylate, a triallyl cyanurate, apolybutadiene, and a phenylenedimaleimide.

In embodiments, the formulation can include solvents selected from thegroup: mineral spirits and hexamethyldi-siloxane.

In embodiments, the formulation can include different first and secondsolvent portions.

The following procedure relates to an order of addition in oneembodiment of a method for making a durable ambient light curablewaterproof liquid rubber formulation.

First, mix 50 percent of the total formulation amount of EPDM polymerand 50 percent of the total formulation amount of mineral spirits (asolvent) in a vessel. Mix the components at a temperature from 20degrees Celsius to 50 degrees Celsius until a smooth homogenous solutionis formed.

Add the remaining 50 percent of the total formulation amount of EPDM tothe solution and continue mixing at a temperature from 20 degreesCelsius to 50 degrees Celsius until all of the EPDM is thoroughly mixedforming a smooth viscous solution.

Into this smooth viscous solution, slowly add 100 percent of the totalamount of filler used in the durable ambient light curable waterproofliquid rubber formulation and 100 percent of the total amount of pigment(if a pigment is used) used in the durable ambient light curablewaterproof liquid rubber formulation.

Once the filler and the pigment (if used) are added, mix at atemperature of from 20 degrees Celsius to 50 degrees Celsius until themixture forms a smooth grind base. The grind base is mixed to from 4 to8 on the Hegman scale.

Add the remaining 50 percent of the total amount of solvent(specifically mineral spirits) used in the durable ambient light curablewaterproof liquid rubber formulation and 100 percent of the total amountof plasticizers used in the durable ambient light curable waterproofliquid rubber formulation to the grind base.

Mix at a temperature from 20 degrees Celsius to 50 degrees Celsius untilall of the solvent and plasticizers are thoroughly incorporated into thesolution.

Add in 100 percent of the total formulation amount of any additives thatmay be used, which can include wetting agents, defoamers, antioxidants,hindered amine light stabilizers, UV absorbers, flame retardants, airrelease agents, biocides, anti-settling agents, pigment dispersants, andadhesion promoters.

Mix at a temperature from 20 degrees Celsius to 50 degrees Celsius untilall of the additives are thoroughly incorporated into the solution. Thesolution is mixed to from 4 to 8 on the Hegman scale.

Into a separate vessel prepare a solution of 100 percent of aphotoinitiator solvent (such as Toluene) and 100 percent of thephotoinitiators used in the durable ambient light curable waterproofliquid rubber formulation.

Mix the photoinitiator solvent and the photoinitiators at a temperaturefrom 20 degrees Celsius to 50 degrees Celsius until all of thephotoinitiators are dissolved and thoroughly mixed into the solution.

Add 100 percent of the total formulation amount of the photoinitiatorssolution to the mixture containing the EPDM, solvent (mineral spirits),filler, pigment, and additives.

Mix at a temperature from 20 degrees Celsius to 50 degrees Celsius untilall of the components are thoroughly incorporated into the solution andthe solution is from 4 to 8 on the Hegman scale. Then add 100 percent ofthe total formulation amount of peroxide curatives.

Following is a list of example components to be used in the method formaking a durable ambient light curable waterproof liquid rubberformulation.

Example 1

Dual Cure Coating Example Component Masterbatch Mix % EPDM TerpolymerT-5131 (2788 Mw) Lot GE2G015 51.28 Filler Coupsil 6508 PrecipitatedSilica 17.96 Solvent Mineral Spirits 20.51 Plasticizer Dow Corning 200Fluid 0.52 Curative 10% Irgacure in Toluene 5.13 Curative 50% IrgacureBP in Toluene 2.05 Curative TBPB 2.56 Viscosity (centipoise) 50000 VOC(gms/L) 249

Example 2

1006-99-1 Component Ingredient % EPDM Terpolymer T-5131 Lot GE2G015(2788 Mw) 44.61 Filler Coupsil 6508 Precipitated Silica 13.38 SolventMineral Spirits 29.74 Plasticizer Dow Corning 200 Fluid 0.45 CurativeIrgacure BP 0.89 Curative Irgacure 819 0.45 Solvent Toluene 4.9 CurativePeroxan PO 2.23 Flame Retardant Trikup ATH 2.23 Pigment Kronos 2300 1.12Viscosity (cP) 5230 VOC (gms/L) 348

Example 3

Component Ingredient % EPDM Terpolymer Trilene 65 Standard 34.1 SolventMineral Spirit 17.05 Solvent HMDS Solvent 17.05 curative Irgacure 8191.7 Solvent Toluene 6.81 Curative Luperox 101 0.57 Pigment TiO₂ 11.36Filler Cupsil 6508 Silica 11.36 Viscosity (cP) >20 K VOC (gms/L) 239

Example 4

Formulation with Defoamer Component Ingredient % EPDM Terpolymer Trilene5131 44.61 Filler Coupsil 6508 3.38 Solvent Mineral Spirits 29.74Plasticizer Dow Corning 200 Fluid 0.45 Curative Irgacure BP 0.89Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative Peroxan PO 2.23Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 Defoamer BYK 052 10.00

Example 5

Formulation with Anti-Settling Agent Component Ingredient % EPDMTerpolymer Trilene 5131 44.61 Filler Coupsil 6508 3.38 Solvent MineralSpirits 29.74 Plasticizer Dow Corning 200 Fluid 0.45 Curative IrgacureBP 0.89 Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative PeroxanPO 2.23 Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 Anti-SettlingAgent MPA 1078 10.00

Example 6

Formulation with a Flame Retardant Component Ingredient % EPDMTerpolymer Trilene 5131 38.61 Filler Coupsil 6508 2.61 Solvent MineralSpirits 19.74 Plasticizer Dow Corning 200 Fluid 0.45 Curative IrgacureBP 0.89 Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative PeroxanPO 2.23 Flame Retardant ATH 30.00 Pigment Kronos 2300 0.12

Example 7

Formulation with a Pigment Dispersant Component Ingredient % EPDMTerpolymer Trilene 5131 44.61 Filler Coupsil 6508 3.38 Solvent MineralSpirits 29.74 Plasticizer Dow Corning 200 Fluid 0.45 Curative IrgacureBP 0.89 Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative PeroxanPO 2.23 Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 PigmentDispersant Nuosperse 9100 10.00

Example 8

Formulation with Biocide Component Ingredient % EPDM Terpolymer Trilene5131 44.61 Filler Coupsil 6508 3.38 Solvent Mineral Spirits 29.74Plasticizer Dow Corning 200 Fluid 0.45 Curative Irgacure BP 0.89Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative Peroxan PO 2.23Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 Biocide Mergal K9N10.00

Example 9

Formulation with an Adhesion Promoter Component Ingredient % EPDMTerpolymer Trilene 5131 44.61 Filler Coupsil 6508 3.38 Solvent MineralSpirits 29.74 Plasticizer Dow Corning 200 Fluid 0.45 Curative IrgacureBP 0.89 Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative PeroxanPO 2.23 Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 AdhesionPromoter SR 634 10.00

Example 10

Formulation with an Air Release Agent Component Ingredient % EPDMTerpolymer Trilene 5131 44.61 Filler Coupsil 6508 3.38 Solvent MineralSpirits 29.74 Plasticizer Dow Corning 200 Fluid 0.45 Curative IrgacureBP 0.89 Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative PeroxanPO 2.23 Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 Air ReleaseAgent Ultra 1199 10.00

Example 11

Formulation with a Wetting Agent Component Ingredient % EPDM TerpolymerTrilene 5131 44.61 Filler Coupsil 6508 3.38 Solvent Mineral Spirits29.74 Plasticizer Dow Corning 200 Fluid 0.45 Curative Irgacure BP 0.89Curative Irgacure 819 0.45 Solvent Toluene 4.90 Curative Peroxan PO 2.23Flame Retardant ATH 2.23 Pigment Kronos 2300 1.12 Wetting Agent BYK 37810.00

While these embodiments have been described with emphasis on theembodiments, it should be understood that within the scope of theappended claims, the embodiments might be practiced other than asspecifically described herein.

What is claimed is:
 1. A method for making a durable ambient lightcurable waterproof liquid rubber formulation with a volatile organiccompound content of less than 450 grams per liter, comprising: a.blending in a closed vessel forming a solution, a first portion ofethylene propylene diene terpolymer (EPDM) with a first portion ofsolvent, wherein the ethylene propylene diene terpolymer (EPDM) is 50weight percent to 99 weight percent of a total amount of ethylenepropylene diene terpolymer used in a resulting durable ambient lightcurable waterproof liquid rubber formulation and the first portion ofsolvents is 33 weight percent to 67 weight percent of a total amount ofsolvent used in the resulting durable ambient light curable waterproofliquid rubber formulation; b. mixing the solution in a high shear mixerfor at least 10 to 240 minutes at a temperature from 20 degrees Celsiusto 50 degrees Celsius forming a high viscosity solution; c. adding asecond portion of ethylene propylene diene terpolymer (EPDM) to the highviscosity solution, wherein the second portion of ethylene propylenediene terpolymer (EPDM) is 0.1 weight percent to 50 weight percent ofthe total amount of ethylene propylene diene terpolymer (EPDM) used inthe resulting durable ambient light curable waterproof liquid rubberformulation; d. adding a second portion of solvent to the high viscositysolution wherein the second portion of solvent is 33 weight percent to80 weight percent of a total amount of solvent used in the resultingdurable ambient light curable waterproof liquid rubber formulation; e.blending the high viscosity solution for 10 minutes to 120 minutes at atemperature from 20 degrees Celsius to 50 degrees Celsius to form a lowviscosity liquid intermediate rubber formulation with a saturatedbackbone of propylene, a saturated backbone of ethylene, and anunsaturated diene with ultra violet activated sites capable ofcrosslinking with or reacting with a free radical or a free radical onanother terpolymer; f. adding 0.1 weight percent to 10 weight percent ofa free radical producing photoinitiator devoid of thermally activatedaccelerators to the low viscosity liquid intermediate rubber formulationbased on the total weight of the resulting dual curable waterproofliquid rubber formulation to generate free radicals that react with theactive sites of the unsaturated diene, forming a low viscosity liquidintermediate rubber formulation with photoinitiator, wherein thephotoinitiators include: Type I photoinitiators including: bis(2,4,6-trimethylbenzoyl)-phenyl phosphineoxide, and1-hydroxy-cyclohexyl-phenyl-ketone; and Type II photoinitiators include:benzophenone, alpha hydroxyl ketone, alpha amino ketone,isothioxanthone, and combinations thereof, and wherein all thephotoinitiators are devoid of thermally activated accelerators; g.adding 0.1 to 15 weight percent of a peroxide to the a low viscosityliquid intermediate rubber formulation with photoinitiator, wherein theperoxide comprises at least one of: a peroxyketal, a peroxyester, adialkyl peroxide, a peroxy carbonate, or an azo initiator forming a dualcure liquid; and h. blending the dual cure liquid at a low shear for 10minutes to 120 minutes at an ambient temperature from 20 degrees Celsiusto 50 degrees Celsius in the absence of light forming the dual ambientlight curable waterproof liquid rubber formulation, wherein the dualambient light curable waterproof liquid rubber formulation is adapted toform a waterproof seal on a substrate in the presence of ambient lightand ambient heat.
 2. The method of claim 1, wherein the first portion ofethylene propylene diene terpolymer has a different molecular weightthan the second portion of ethylene propylene diene terpolymer.
 3. Themethod of claim 1, comprising: a. adding to the high viscosity solutionat a temperature from 20 degrees Celsius to 50 degrees Celsius at leastone of: (i) 50 weight percent to 99 weight percent of a pigment; and(ii) 50 weight percent to 99 weight percent of a filler; and wherein theamount of the pigment and the filler added represent a total weightpercent of pigment and filler in the high viscosity solution; and b.blending the pigment and filler to a particle dispersion from 4 to 8units on the Hegman scale.
 4. The method of claim 1, further comprisingadding to the low viscosity liquid intermediate 0.1 weight percent to 10weight percent of additives based on a total weight of the resultingdurable ambient light curable waterproof liquid rubber formulation andthe additives are at least one of: a hindered phenolic stabilizer or ahindered amine ultraviolet stabilizer.
 5. The method of claim 1, furthercomprising adding to the low viscosity liquid intermediate 0.1 weightpercent to 10 weight percent of an adhesion promoter based on the totalweight of the resulting durable ambient light curable waterproof liquidrubber formulation after adding the second portion of ethylene propylenediene terpolymer (EPDM) to the high viscosity solution, wherein theadhesion promoter is at least one of: a zinc diacrylate or zincdimethacrylate.
 6. The method of claim 1, further comprising adding tothe low viscosity liquid intermediate rubber formulation: 0.1 weightpercent to 10 weight percent of a pigment dispersant based on the totalweight of the resulting durable ambient light curable waterproof liquidrubber formulation, wherein the pigment dispersant is1methoxy-2-propylacetate.
 7. The method of claim 1, further comprisingadding to the low viscosity liquid intermediate rubber formulation: 0.1weight percent to 10 weight percent of an anti-settling agent based onthe total weight of the resulting durable ambient light curablewaterproof liquid rubber formulation, wherein the anti-settling agent isat least one of a hydroxyl ethyl cellulose and a fumed silica.
 8. Themethod of claim 1, further comprising adding to the low viscosity liquidintermediate rubber formulation 0.1 weight percent to 10 weight percentof a defoamer based on the total weight of the resulting durable ambientlight curable waterproof liquid rubber formulation, and wherein thedefoamer is at least one of: a polymethyl alkyl siloxane, a modifiedpolysiloxane, and a polymethylsiloxane in a solvent.
 9. The method ofclaim 1, further comprising adding to the low viscosity liquidintermediate rubber formulation 0.1 weight percent to 10 weight percentof an air release agent based on the total weight of the resultingdurable ambient light curable waterproof liquid rubber formulation,wherein the air release agent comprises at least one of: a mineral oil,a paraffinic oil, a silicone oil, or a similar oil.
 10. The method ofclaim 3, further comprising adding 0.1 weight percent to 30 weightpercent of a flame retardant to low viscosity liquid intermediate rubberformulation, based on the total weight of the resulting durable ambientlight curable waterproof liquid rubber formulation, wherein the flameretardant comprises: an alumina trihydrate, by adding: a. with a memberof at least one of: a pigment, a filler, and an additives to the lowviscosity liquid intermediate rubber formulation; or b. after the secondportion of ethylene propylene diene terpolymer is added to the highviscosity solution.
 11. The method of claim 1, further comprising addingto the low viscosity liquid intermediate rubber formulation 0.1 weightpercent to 12 weight percent of a wetting agent based on the totalweight of the resulting durable ambient light curable waterproof liquidrubber formulation, wherein the wetting agent is at least one of: asilicone polyacrylate copolymer in solvent and a solvent-free polyethermodified dimethylpolysiloxane.
 12. The method of claim 1, furthercomprising adding to the low viscosity liquid intermediate rubberformulation 0.1 weight percent to 10 weight percent of a biocide basedon the total weight of the resulting durable ambient light curablewaterproof liquid rubber formulation, wherein the biocide is amethylchloroisothiazolinone.
 13. The method of claim 1, furthercomprising adding 0.1 weight percent to 30 weight percent of a lowmolecular weight non-volatile plasticizer low viscosity liquidintermediate rubber formulation after the second portion of solvent isadded to the high shear mixture, wherein the low molecular weightnon-volatile plasticizer comprises: a paraffinic oil, naphthenic oil,plant based oil, diester oil, silicone oil, a mineral oil, a lowmolecular weight polyalphaolefin, or combinations thereof.
 14. Themethod of claim 1, further comprising adding 0.01 weight percent to 10weight percent of a co-agent to the low viscosity liquid intermediaterubber formulation based on a total weight of the resulting dual curablewaterproof liquid rubber formulation of a co-agent to the second lowviscosity liquid intermediate rubber formulation, wherein the co-agentcomprises at least one of: an acrylate, a triallyl cyanurate, apolybutadiene, or a phenylenedimaleimide.
 15. The method of claim 1,wherein the first portion of solvent and the second portion of solventare selected from the group: mineral spirits and hexamethyldi-siloxane.16. The method of claim 15, wherein the first portion of solvent and thesecond portion of solvent are different solvents.